A dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property and a preparation method thereof

Abstract

The invention discloses a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property and a preparation method thereof. The invention comprises the following steps: adding polyethylene glycol monomethyl ether and sulfonyl chloride substances into a first reaction container, adding a solvent chloroalkane to fully dissolve the substances; adding a weak base, reacting at room temperature, and collecting to obtain a pale yellow liquid crude product; extracting, rotary evaporating, and drying the pale yellow liquid crude product to obtain a pale yellow intermediate product sulfonate; adding sodium hydride and 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol into a second reaction container, adding ultra-dry tetrahydrofuran into the second reaction container, stirring the reaction, and then adding the mixture into the reaction container. The light yellow intermediate product sulfonate is added to the second reaction container, and the temperature is raised to 65-85°C for reaction; after the reaction is completed, the temperature is lowered to 15-25°C, and an orange-red liquid crude product is collected; the orange-red liquid crude product is extracted with dichloromethane or ethyl acetate, rotary evaporated, and dried, and then column chromatography is performed to obtain a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant; as an additive for wet electronic chemicals in the semiconductor and new display fields, the surface tension of the wet electronic chemicals, the contact angle between the wet electronic chemicals and the substrate, and the foaming amount can be effectively reduced after addition, thereby improving the product yield.

Description

Technical Field

[0001] The invention relates to the technical field of surfactants, and in particular to a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property and a preparation method thereof. Background Art

[0002] Wet electronic materials used in the semiconductor and new display fields mainly include etching solutions, stripping solutions and cleaning solutions, which are generally used in etching, wafer surface cleaning and other processes in the manufacturing process of integrated circuits and display panels. As the feature size of integrated circuit process transistors becomes finer and finer, the integrated circuit process technology has now developed to advanced nanoscale technology. As a result, the technical requirements for wet electronic chemicals such as cleaning solutions, developers and stripping solutions have also gradually increased, especially the surface tension of wet electronic chemicals and their wettability in contact with the substrate surface. During the exposure and development process of photoresist, microstructures will be formed. Due to its excessive surface tension, the developer's wettability to the photoresist is weakened, resulting in weak or no display. Adding traditional surfactants to the developer is prone to produce a large amount of foam. The presence of foam interferes with the reaction of the reactive group with the dilute alkaline solution, resulting in incomplete dissolution of the residue in the unexposed part, reducing the development quality, and then resulting in poor effects and low chip production yield.

[0003] The low surface tension and low foaming dodecyne-based nonionic Gemini surfactant is a surfactant suitable for wet electronic chemicals in the semiconductor and new display fields. It can effectively reduce the surface tension of wet electronic chemicals when added in a small amount. At the same time, it has strong wettability, which is conducive to the uniform and full contact between wet electronic chemicals and the surface to be treated, thereby reducing the occurrence of defects in the manufacturing process of semiconductor display panels, etc. In addition, nonionic surfactants have low foaming properties and excellent resistance to strong alkali and strong acid environments and high stability.

[0004] Patent CN1126716A discloses ethoxylated acetylenic diols with low dynamic surface tension, the structure of which contains hydroxyl-terminated polyoxyethylene chains, with the number of ethoxylated moles per mole of acetylenic diol being 4-12. The substance has outstanding wetting properties, and the decontamination ability and foam volume increase with the increase in the number of ethoxy groups. However, its foaming property is relatively large, making it difficult to adapt to wet electronic chemicals in the semiconductor and new display fields. Patent CN103965461A discloses a method for synthesizing acetylene glycol polyoxyethylene ether, wherein 2,4,7,9-tetramethyl-5-decyne-4,7-diol and ethylene oxide are used as raw materials to prepare 2,4,7,9-tetramethyl-5-decyne-4,7-diol polyoxyethylene ether having a hydrophilic end as a hydroxyl group through a polymerization reaction, wherein the number of moles of ethoxylation in each mole of acetylene glycol polyoxyethylene ether is 1-52. However, the substance has a large foaming property and is difficult to be adapted to wet electronic chemicals in the semiconductor and new display fields. At the same time, ethylene oxide is used as a raw material in the reaction process, and high temperature and high pressure may be involved, which is very dangerous. Summary of the invention

[0005] The object of the present invention is to provide a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property and a preparation method thereof, so as to overcome the deficiencies in the prior art.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] The present application discloses a method for preparing a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property, which specifically comprises the following steps:

[0008] S1, adding polyethylene glycol monomethyl ether and sulfonyl chloride substances into a reaction vessel 1, and then adding a solvent chloroalkane to fully dissolve them;

[0009] S2. Add a weak base to the reaction vessel 1, react at room temperature for 18 to 36 hours, and collect a pale yellow liquid crude product;

[0010] S3, extracting the pale yellow crude liquid product obtained in step S2 with dichloromethane or ethyl acetate, rotary evaporating, and drying to obtain a pale yellow intermediate product sulfonate;

[0011] S4, adding sodium hydride and 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to reaction vessel 2, replacing the air in reaction vessel 2 with inert gas; adding ultra-dry tetrahydrofuran to reaction vessel 2, stirring and reacting for 20 to 40 minutes, adding the light yellow intermediate product sulfonate obtained in step S3 to reaction vessel 2, and heating to 65 to 85° C. to react for 36 to 48 hours; after the reaction is completed, lowering the temperature to 15 to 25° C., and collecting to obtain an orange-red liquid crude product;

[0012] S5. The orange-red liquid crude product obtained in step S4 is extracted with dichloromethane or ethyl acetate, subjected to rotary evaporation and drying treatment, and then subjected to column chromatography to obtain a dodecynyl nonionic Gemini surfactant with low surface tension and low foaming properties.

[0013] Preferably, in step S1, the molar ratio of polyethylene glycol monomethyl ether to sulfonyl chloride is 1:1-2; the sulfonyl chloride is selected from p-toluenesulfonyl chloride, methylsulfonyl chloride or tetra-tert-butylbenzenesulfonyl chloride; the chloroalkane is selected from dichloromethane, chloroform or dichloroethane.

[0014] Preferably, the molecular weight of polyethylene glycol monomethyl ether in step S1 is 200-500.

[0015] Preferably, the weak base in step S2 is an organic amine substance, including one of triethylamine, triethylenediamine or diisopropylethylamine.

[0016] Preferably, the molar ratio of the polyethylene glycol monomethyl ether to the organic amine substance is 1:2-3.

[0017] Preferably, in step S4, the molar ratio of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to sodium hydride is 1:2-4.

[0018] Preferably, in step S4, the molar ratio of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to the light yellow intermediate product sulfonate is 1:2-3.

[0019] The present invention also discloses a low surface tension and low foaming dodecylene-based nonionic Gemini surfactant, which is prepared by the above-mentioned method for preparing a low surface tension and low foaming dodecylene-based nonionic Gemini surfactant; the structural formula is as follows: Where n is a natural number.

[0020] Preferably, n is 4-10.

[0021] Beneficial effects of the present invention:

[0022] 1. The product of the present invention is a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property. As a surfactant additive for wet electronic chemicals in the semiconductor and new display fields, adding a small amount can effectively reduce the surface tension and contact angle of wet electronic chemicals and enhance the ability to wet the substrate. Moreover, it is a nonionic surfactant and does not introduce impurities such as metal ions;

[0023] 2. The hydrophilic group tail of the dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property of the present invention is terminated with a methyl group. The presence of the methyl group increases the molecular area of ​​the surfactant at the gas-liquid interface, and the formed non-copolymer film is unstable, so that the foaming amount of the surfactant is reduced, which can improve the problem of reduced development quality caused by high foaming amount of the developer;

[0024] 3. The method for preparing a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property uses normal pressure reaction conditions and polyethylene glycol monomethyl ether with different average molecular weights to replace high temperature and high pressure environment and flammable and explosive liquid ethylene oxide, which is safe, simple and practical.

[0025] 4. The polyoxyethylene ether chain length of the dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property of the present invention is moderate, thereby avoiding the problem of poor solubility in aqueous solution system caused by too short polyoxyethylene ether chain length;

[0026] 5. The low surface tension and low foaming dodecyne-based nonionic Gemini surfactant of the present invention has different molecular weights. Gemini surfactants of different molecular weights correspond to different surface properties and wettability, and can be adapted to various application scenarios of wet electronic chemicals;

[0027] 6. The low surface tension and low foaming dodecyne-based nonionic Gemini surfactant of the present invention has low surface tension and excellent wettability, so that the wet electronic chemicals added with this surfactant can be in uniform and sufficient contact with the surface to be treated, which is beneficial to reduce the insufficient contact between the wet electronic chemical materials and the target film layer in the manufacturing process of semiconductor display panels, and further reduce the problems of poor effect and low chip production yield in the cleaning, development and stripping processes.

[0028] 7. The special structure of the dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property of the present invention makes it easy to adsorb tightly on the gas / liquid surface, with higher ability to reduce surface tension, extremely low CMC, excellent wetting performance, and excellent properties such as resistance to strong alkaline and strong acidic environment and high stability. It can be adapted to various wet electronic chemicals such as developers and etching solutions in the semiconductor and new display fields.

[0029] 8. The low surface tension and low foaming dodecyne-based nonionic Gemini surfactant of the present invention does not contain toxic elements such as fluorine and is environmentally friendly.

[0030] The features and advantages of the present invention will be described in detail through embodiments in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1This is an infrared spectrum of a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant (n=4) in Example 1;

[0032] Figure 2 This is the 1HNMR spectrum of a dodecyne-based nonionic Gemini surfactant (n=4) with low surface tension and low foaming properties in Example 1;

[0033] Figure 3 It is a contact angle diagram before and after adding a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant (n=4) to the developer;

[0034] Figure 4 This is an infrared spectrum of a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant (n=8) in Example 2;

[0035] Figure 5 This is the 1HNMR spectrum of a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant (n=8) in Example 2;

[0036] Figure 6 It is a contact angle diagram before and after adding a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant (n=8) to the developer;

[0037] Figure 7 This is an infrared spectrum of a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant (n=10) of Example 3;

[0038] Figure 8 This is the 1HNMR spectrum of a dodecyne-based nonionic Gemini surfactant (n=10) with low surface tension and low foaming properties in Example 3;

[0039] Fig. 9 The figure is the contact angle diagram before and after adding a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant (n=10) into the developer. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described in detail below through the accompanying drawings and embodiments. However, it should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the scope of the present invention. In addition, in the following description, the description of known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present invention.

[0041] The embodiment of the present invention provides a method for preparing a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property, which specifically comprises the following steps:

[0042] S1, adding polyethylene glycol monomethyl ether and sulfonyl chloride substances into a reaction vessel 1, and then adding a solvent chloroalkane to fully dissolve them;

[0043] S2. Add a weak base to the reaction vessel 1, react at room temperature for 18 to 36 hours, and collect a pale yellow liquid crude product;

[0044] S3, extracting the pale yellow crude liquid product obtained in step S2 with dichloromethane or ethyl acetate, rotary evaporating, and drying to obtain a pale yellow intermediate product sulfonate;

[0045] S4, adding sodium hydride and 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to reaction vessel 2, replacing the air in reaction vessel 2 with inert gas; adding ultra-dry tetrahydrofuran to reaction vessel 2, stirring and reacting for 20 to 40 minutes, adding the light yellow intermediate product sulfonate obtained in step S3 to reaction vessel 2, and heating to 65 to 85° C. to react for 36 to 48 hours; after the reaction is completed, lowering the temperature to 15 to 25° C., and collecting to obtain an orange-red liquid crude product;

[0046] S5. The orange-red liquid crude product obtained in step S4 is extracted with dichloromethane or ethyl acetate, subjected to rotary evaporation and drying treatment, and then subjected to column chromatography to obtain a dodecynyl nonionic Gemini surfactant with low surface tension and low foaming properties.

[0047] In a feasible embodiment, in step S1, the molar ratio of polyethylene glycol monomethyl ether to sulfonyl chloride is 1:1-2; the sulfonyl chloride is selected from p-toluenesulfonyl chloride, methylsulfonyl chloride or tetra-tert-butylbenzenesulfonyl chloride; the chloroalkane is selected from dichloromethane, chloroform or dichloroethane.

[0048] In a feasible embodiment, the molecular weight of polyethylene glycol monomethyl ether in step S1 is 200-500.

[0049] In a feasible embodiment, the weak base in step S2 is an organic amine substance, including one of triethylamine, triethylenediamine or diisopropylethylamine.

[0050] In a feasible embodiment, the molar ratio of the polyethylene glycol monomethyl ether to the organic amine substance is 1:2-3.

[0051] In a feasible embodiment, in step S4, the molar ratio of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to sodium hydride is 1:2-4.

[0052] In a feasible embodiment, in step S4, the molar ratio of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to the light yellow intermediate product sulfonate is 1:2-3.

[0053] The present invention discloses a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property, and the structural formula is as follows:

[0054] Where n is a natural number.

[0055] In a feasible embodiment, the n is 4-10.

[0056] The preparation method of the embodiment of the present invention is shown in the following formula:

[0057]

[0058] The reactants are polyethylene glycol monomethyl ether, sulfonyl chloride substances, and 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol; R in the sulfonyl chloride substances is one of p-tolyl, methyl or tetra-tert-butylphenyl; the weak base is an organic amine substance, which is one of triethylamine, triethylenediamine, and diisopropylethylamine; the solvent is a chlorinated alkane, which is one of dichloromethane, chloroform or dichloroethane; THF is ultra-dry tetrahydrofuran, and NaH is sodium hydride.

[0059] Embodiment 1:

[0060] First, 20 g of polyethylene glycol monomethyl ether with an average molecular weight of 200 and p-toluenesulfonyl chloride (the molar ratio of polyethylene glycol monomethyl ether to p-toluenesulfonyl chloride is 1:1) are added to a round-bottom flask, and solvent dichloromethane is added to fully dissolve it. Triethylamine (the molar ratio of polyethylene glycol monomethyl ether to triethylamine is 1:2) is added to the reaction system at a uniform speed using a syringe, and the reaction is carried out at room temperature for 18 hours. A pale yellow liquid crude product is collected, and then the crude product is extracted with dichloromethane, and then rotary evaporated and dried to obtain a pale yellow intermediate product sulfonate. 2 g of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol and sodium hydride (2,5,8,11-tetramethyl-6-dodecyne-5,8-diol and sodium hydride) are added in an inert gas atmosphere. The molar ratio of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to p-toluenesulfonate is 1:2) and added to a three-necked flask, the air in the three-necked flask is replaced by an inert gas, ultra-dry tetrahydrofuran is added to the reaction vessel, and the reaction is carried out for 30 minutes under magnetic stirring; p-toluenesulfonate (the molar ratio of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to p-toluenesulfonate is 1:2) dissolved in ultra-dry tetrahydrofuran is slowly injected into the reaction system with a syringe; the reaction system is heated to 65°C and reacted for 48 hours; the reaction temperature is reduced to 15°C, and an orange-red liquid crude product is collected; the crude product is extracted with dichloromethane, and then dried by rotary evaporation again, and then a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming is obtained by column chromatography.

[0061] like Figure 1 As shown, the infrared spectrum of this embodiment:

[0062] 2870cm -1 (peak1) is the stretching vibration absorption peak of methyl group; 1463cm -1 (peak2) is the bending vibration absorption peak of saturated CH (methyl and methylene); 1368cm -1 (peak3) is the bending vibration absorption peak of methyl group; 1304cm -1 (peak4) is the bending vibration absorption peak of -CH2 in the -[-O-CH2-CH2-O-]- segment; 1108cm -1 (peak5) COC on the polyoxyethylene chain is the stretching vibration absorption peak.

[0063] like Figure 2 As shown, in this embodiment 1 HNMR spectrum;

[0064] 1HNMR (500MHz, CDCl3) δ3.93–3.46 (m, 31H), 3.41 (d, J=10.1Hz, 6H), 1.74–1.52 (m, 6H), 1.48–1.21 (m, 10H), 0.96–0.87 (m, 12H).

[0065] like Figure 3 As shown, the contact angle diagram before and after this embodiment; from the comparison of the figures, it can be seen that after adding low surface tension and low foaming dodecyne-based non-ionic Gemini surfactant to the developer, its interfacial contact angle becomes smaller, indicating that the wettability of the developer is enhanced.

[0066] Embodiment 2:

[0067] First, 20 g of polyethylene glycol monomethyl ether with an average molecular weight of 350 and methyl sulfonyl chloride (the molar ratio of polyethylene glycol monomethyl ether to methyl sulfonyl chloride is 1:1.6) are added to a round-bottom flask, and solvent chloroform is added to fully dissolve it. Triethylene diamine (the molar ratio of polyethylene glycol monomethyl ether to triethylene diamine is 1:3) is added to the reaction system with a syringe at a uniform speed. The reaction is carried out at room temperature for 27 hours, and a pale yellow liquid crude product is collected. The crude product is then extracted with dichloromethane, and then rotary evaporated and dried to obtain a pale yellow intermediate product sulfonate. 2 g of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol and sodium hydride (2,5,8,11-tetramethyl-6-dodecyne-5,8-diol and sodium hydride) are added to the reaction system in an inert gas atmosphere. The method comprises the following steps: adding 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to methyl sulfonate in a molar ratio of 1:3) into a three-necked flask, replacing the air in the three-necked flask with an inert gas, adding ultra-dry tetrahydrofuran into a reaction vessel, and reacting for 40 minutes under magnetic stirring; slowly injecting methyl sulfonate (the molar ratio of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to methyl sulfonate is 1:2.6) dissolved in ultra-dry tetrahydrofuran into the reaction system with a syringe; heating the reaction system to 75°C and reacting for 42 hours; lowering the reaction temperature to 20°C, and collecting an orange-red liquid crude product; extracting the crude product with ethyl acetate, and then performing rotary evaporation to dry it again, and then obtaining a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property through column chromatography.

[0068] like Figure 4 As shown, the infrared spectrum of this embodiment:

[0069] 2870cm -1 (peak1) is the stretching vibration absorption peak of methyl group; 1463cm -1 (peak2) is the bending vibration absorption peak of saturated CH (methyl and methylene); 1353 cm -1 (peak3) is the bending vibration absorption peak of methyl group; 1301cm-1 (peak4) is the bending vibration absorption peak of -CH2 in the -[-O-CH2-CH2-O-]- segment; 1109cm -1 (peak5) COC on the polyoxyethylene chain is the stretching vibration absorption peak.

[0070] like Figure 5 As shown, in this embodiment 1 HNMR spectrum;

[0071] 1 HNMR (500MHz, CDCl3) δ3.72–3.55 (m, 64H), 3.39 (s, 6H), 1.73–1.49 (m, 6H), 1.43–1.27 (m, 10H), 0.90 (d, J=6.5Hz, 12H).

[0072] like Figure 6 As shown, the contact angle diagram before and after this embodiment; from the comparison of the figures, it can be seen that after adding low surface tension and low foaming dodecyne-based non-ionic Gemini surfactant to the developer, its interfacial contact angle becomes smaller, indicating that the wettability of the developer is enhanced.

[0073] Embodiment 3:

[0074] First, 20g of polyethylene glycol monomethyl ether with an average molecular weight of 500 and tetra-tert-butylbenzenesulfonyl chloride (the molar ratio of polyethylene glycol monomethyl ether to tetra-tert-butylbenzenesulfonyl chloride is 1:2) are added to a round-bottom flask, and solvent dichloroethane is added to fully dissolve it. Diisopropylethylamine (the molar ratio of polyethylene glycol monomethyl ether to diisopropylethylamine is 1:2.5) is added to the reaction system at a uniform speed using a syringe. The reaction is carried out at room temperature for 36 hours, and a pale yellow liquid crude product is collected. The crude product is then extracted with dichloromethane, and then rotary evaporated and dried to obtain a pale yellow intermediate product sulfonate. 2g of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol and sodium hydride (2,5,8,11-tetramethyl-6-dodecyne-5,8-diol) are added to the reaction system in an inert gas atmosphere. The method comprises the following steps: adding 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol (the molar ratio of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to tetra-tert-butylbenzene sulfonate is 1:3) dissolved in ultra-dry tetrahydrofuran into the reaction system; heating the reaction system to 85°C and reacting for 36 hours; lowering the reaction temperature to 25°C and collecting an orange-red liquid crude product; extracting the crude product with dichloromethane, and then performing rotary evaporation to dry it, and then obtaining a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property through column chromatography.

[0075] like Figure 7 As shown, the infrared spectrum of this embodiment:

[0076] 2869cm -1 (peak1) is the stretching vibration absorption peak of methyl group; 1463cm -1 (peak2) is the bending vibration absorption peak of saturated CH (methyl and methylene); 1352cm -1 (peak3) is the bending vibration absorption peak of methyl group; 1301cm -1 (peak4) is the bending vibration absorption peak of -CH2 in the -[-O-CH2-CH2-O-]- segment; 1108cm -1 (peak5) COC on the polyoxyethylene chain is the stretching vibration absorption peak.

[0077] like Figure 8 As shown, in this embodiment 1 HNMR spectrum;

[0078] 1HNMR (400MHz, CDCl3) δ3.71–3.55 (m, 81H), 3.38 (s, 6H), 1.72–1.50 (m, 6H), 1.39–1.26 (m, 10H), 0.89 (d, J=6.6Hz, 12H).

[0079] like Fig. 9 As shown, the contact angle diagram before and after this embodiment; from the comparison of the figures, it can be seen that after adding low surface tension and low foaming dodecyne-based non-ionic Gemini surfactant to the developer, its interfacial contact angle becomes smaller, indicating that the wettability of the developer is enhanced.

[0080] Table 1 shows the contact angle and surface tension data before and after adding low surface tension and low foaming dodecyne-based nonionic Gemini surfactant (concentration of 0.001 mol / L) into the semiconductor display wet electronic chemical developer.

[0081]

[0082] It can be seen from the data in the table that after the addition of the low surface tension and low foaming dodecyne-based nonionic Gemini surfactant, the contact angle and surface tension of the developer solution are significantly reduced.

[0083] Foaming test: The initial foaming volume is used to measure the foaming ability of the surfactant solution; a surfactant solution with a concentration of 1g / L is prepared, 5mL of the surfactant solution is added to a 25mL stoppered measuring cylinder, and foam is generated by shaking the measuring cylinder up and down 20 times, and the volume of foam generated (mL) is immediately recorded.

[0084] Table 2 shows the foaming results of the low surface tension and low foaming dodecynyl nonionic Gemini surfactant and the corresponding hydroxyl-terminated dodecynyl nonionic Gemini surfactant of the present invention:

[0085]

[0086] It can be seen from the data in the table that for surfactants with the same number of ethylene oxides, the dodecynyl nonionic Gemini surfactant solution of the present invention has a smaller initial foaming volume and lower foaming property than the hydroxyl-terminated dodecynyl nonionic Gemini surfactant. This is because compared with the terminal hydroxyl-terminated surfactant, the presence of the terminal methyl group makes the surfactant have a larger molecular area at the gas-liquid interface, forming a loosely arranged non-copolymer film, so that the foaming property is lower.

[0087] Table 3 is an evaluation of the development results before and after adding the low surface tension and low foaming dodecynyl nonionic Gemini surfactant (concentration of 0.001 mol / L) of the present invention and the corresponding hydroxyl-terminated dodecynyl nonionic Gemini surfactant (concentration of 0.001 mol / L) to the semiconductor display wet electronic chemical developer;

[0088]

[0089] Evaluation criteria for development results: A indicates uniform development, B indicates uneven development of some areas, and C indicates uneven development. It can be seen from the data in the table that after the low surface tension and low foaming dodecynyl nonionic Gemini surfactant is added to the developer, the development result is significantly improved, while after the corresponding hydroxyl-terminated dodecynyl nonionic Gemini surfactant is added, only the hydroxyl-terminated dodecynyl nonionic Gemini surfactant with n=4 can improve the development effect.

[0090] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modification, equivalent substitution or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming properties, characterized in that: The specific steps include: S1, adding polyethylene glycol monomethyl ether and sulfonyl chloride substances into a reaction vessel 1, and then adding a solvent chloroalkane to fully dissolve them; the sulfonyl chloride substance is selected from p-toluenesulfonyl chloride, methanesulfonyl chloride or 4-tert-butylbenzenesulfonyl chloride; S2. Add a weak base to the reaction vessel 1, react at room temperature for 18-36 hours, and collect a pale yellow liquid crude product; S3, extracting the pale yellow crude liquid product obtained in step S2 with dichloromethane or ethyl acetate, rotary evaporating, and drying to obtain a pale yellow intermediate product sulfonate; S4, adding sodium hydride and 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to reaction vessel 2, replacing the air in reaction vessel 2 with inert gas; adding ultra-dry tetrahydrofuran to reaction vessel 2, stirring and reacting for 20-40 minutes, adding the light yellow intermediate product sulfonate obtained in step S3 to reaction vessel 2, and heating to 65-85°C to react for 36-48 hours; after the reaction is completed, lowering the temperature to 15-25°C, and collecting to obtain an orange-red liquid crude product; S5. The orange-red liquid crude product obtained in step S4 is extracted with dichloromethane or ethyl acetate, subjected to rotary evaporation, and dried, and then subjected to column chromatography to obtain a dodecynyl nonionic Gemini surfactant with low surface tension and low foaming properties; the structural formula of the surfactant is as follows: , where n is 4~10.

2. The method for preparing a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant according to claim 1, characterized in that: In step S1, the molar ratio of polyethylene glycol monomethyl ether to sulfonyl chloride is 1:1-2; the chloroalkane is selected from dichloromethane, chloroform or dichloroethane.

3. The method for preparing a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant according to claim 1, characterized in that: The molecular weight of polyethylene glycol monomethyl ether in step S1 is 200-500.

4. The method for preparing a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant according to claim 1, characterized in that: In step S2, the weak base is an organic amine selected from triethylamine, triethylenediamine or diisopropylethylamine.

5. The method for preparing a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant according to claim 3, characterized in that: The molar ratio of the polyethylene glycol monomethyl ether to the organic amine substance is 1:2-3.

6. The method for preparing a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant according to claim 1, characterized in that: In step S4, the molar ratio of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to sodium hydride is 1:2-4.

7. The method for preparing a low surface tension and low foaming dodecyne-based nonionic Gemini surfactant according to claim 1, characterized in that: In step S4, the molar ratio of 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol to the light yellow intermediate product sulfonate is 1:2-3.

8. A low surface tension and low foaming dodecyne-based nonionic Gemini surfactant, characterized in that: The method for preparing a dodecyne-based nonionic Gemini surfactant with low surface tension and low foaming property as described in any one of claims 1 to 7 is used to prepare the surfactant; the structural formula is as follows: , where n is 4~10.

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